EP4153710A1 - Soil release polyesters for use in detergent compositions - Google Patents
Soil release polyesters for use in detergent compositionsInfo
- Publication number
- EP4153710A1 EP4153710A1 EP21726646.9A EP21726646A EP4153710A1 EP 4153710 A1 EP4153710 A1 EP 4153710A1 EP 21726646 A EP21726646 A EP 21726646A EP 4153710 A1 EP4153710 A1 EP 4153710A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixtures
- formula
- linear
- group
- structural units
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 178
- 229920000728 polyester Polymers 0.000 title claims abstract description 101
- 239000002689 soil Substances 0.000 title claims abstract description 35
- 239000003599 detergent Substances 0.000 title claims description 73
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 229960004063 propylene glycol Drugs 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 9
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- -1 capryl) Chemical group 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000002736 nonionic surfactant Substances 0.000 description 11
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 108090000790 Enzymes Proteins 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 8
- 239000000872 buffer Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 229940088598 enzyme Drugs 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 150000008051 alkyl sulfates Chemical class 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 150000004996 alkyl benzenes Chemical class 0.000 description 6
- 239000003352 sequestering agent Substances 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003752 hydrotrope Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 239000002888 zwitterionic surfactant Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940093476 ethylene glycol Drugs 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002169 ethanolamines Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
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- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- DRLIOHVXDBLHQM-UHFFFAOYSA-N 1-amino-3-(2-methoxyethoxy)propan-2-ol Chemical compound COCCOCC(O)CN DRLIOHVXDBLHQM-UHFFFAOYSA-N 0.000 description 1
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- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
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- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012753 anti-shrinkage agent Substances 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 108010055059 beta-Mannosidase Proteins 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- IBOBFGGLRNWLIL-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)[O-] IBOBFGGLRNWLIL-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 108010087558 pectate lyase Proteins 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Definitions
- the invention relates to specific polyesters, a process for their preparation, their use as soil release agents, their use in detergent compositions, detergent compositions comprising the polyesters and surfactants and solutions or dispersions comprising the polyesters.
- Polyester containing fabrics can be surface modified to increase the hydrophilicity of the fabric, which can improve soil removal.
- Such surface modification can be achieved through direct treatment of the fabric, as outlined for example in GB 1 ,088,984, or more preferably through deposition of a surface modifying polymer in a washing process, as disclosed for example in US 3,962,152.
- the renewable soil release finish imparted through washing ensures the continuous protection of the fiber from oily stains.
- the polymers used in these processes typically consist of a polyester midblock with either one or two endblocks of polyethylene glycol, as further outlined in US 3,959,230 and US 3,893,929.
- anionic moieties in the polymer structure is known to improve the efficacy of these soil release polymers and in particular, improve their anti redeposition properties.
- DE 102007013217 and EP 1 966273 disclose anionic polyesters that may be used as soil release agents in laundry detergents. Such anionic soil release polymers are particularly well suited for use in powder detergents due to their handling properties and compatibility with the detergent composition.
- US 4,711 ,730, US 4,713,194 and US 4,759,876 disclose aqueous detergent compositions containing soil release polymers.
- a typical property of existing soil release polymers described in the prior art is their tendency to significantly reduce the viscosity of detergent compositions. While comparatively low viscosities of concentrates to be used for the preparation of detergent compositions are advantageous for their handling, e.g. with regard to pumpability or dosage consistency, end-consumers tend to correlate higher viscosities of detergent compositions with better performance.
- the formulator must add additional components to the detergent composition to regain this viscosity. The latter is non-ideal as this can bring additional costs and effort. Moreover, the use of additional materials is not preferred from an environmental aspect.
- polyesters comprising one or more structural units of the formula (I) and one or more structural units of the formula (II) and one or more terminal groups of the formula (lll-a) or mixtures thereof (lll-a) wherein
- R 1 is a linear or branched, preferably a linear, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 18 carbon atoms or mixtures thereof, and more preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 15 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, preferably from 10 to 200, more preferably from 20 to 150 and even
- R 2 is a linear or branched alkylene group (Cmhtem) with m being a number from 2 to 10 or mixtures thereof, preferably with m being a number from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (C3H6), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (C3H6) and mixtures thereof, and particularly preferably is (C2H4).
- Cmhtem linear or branched alkylene group
- polyesters comprising one or more structural units of the formula (I) and one or more structural units of the formula (II) and one or more terminal groups of the formula (lll-a) or mixtures thereof
- R 1 is a linear or branched, preferably a linear, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 18 carbon atoms or mixtures thereof, and more preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 15 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, preferably from
- R 2 is a linear or branched alkylene group (Cmhtem) with m being a number from 2 to 10 or mixtures thereof, preferably with m being a number from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (C3H6), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (C3H6) and mixtures thereof, and particularly preferably is (C2H4).
- Cmhtem linear or branched alkylene group
- the polyesters of the invention possess or lead to advantageous soil release and viscosity properties and preferably do not reduce or even increase the viscosity of detergent compositions.
- the inventive polyesters additionally e.g. show beneficial compatibility with liquid detergent compositions, detergency enhancement, advantageous hydrolysis stability, and beneficial anti-greying effects.
- EP 0442 101 discloses polyesters containing nonionic surfactants in a condensed form, their preparation and their use in detergents.
- WO 97/30141 discloses polyetherestercarbonate as dirt dissolving polymers in washing and textile adjuvants.
- WO 95/32232 discloses soil release polymers that effectively remove greasy soils.
- the one or more structural units of the formula (I) of the polyesters of the invention are derived from terephthalic acid or its salts or its dialkyl esters, preferably its (Ci-C4)-dialkyl esters and more preferably its dimethyl ester, or mixtures thereof.
- polyesters of the invention can be used in the polyesters of the invention, such as, phthalic acid, isophthalic acid, 5-sulfoisophthalic acid, 3-sulfophthalic acid, 4-sulfophthalic acid, naphthalene-1 ,4-dicarboxylic acid, naphthalene-2, 6, -dicarboxylic acid, tetrahydrophthalic acid, trimellitic acid, diphenoxyethane-4, 4' -dicarboxylic acid, diphenyl-4, 4'-dicarboxylic acid, 2,5-furandicarboxylic acid, adipic acid, sebacic acid, decan-1 ,10-dicarboxylic acid, fumaric acid, succinic acid, 1.4-cyclohexanedicarboxylic acid, cyclohexanedia
- the one or more structural units of the formula (II) of the polyesters of the invention are derived from 1,2-propyleneglycol.
- further structural units derived from triols or tetraols can be used in the polyesters of the invention, such as, glycerol, pentaerythritol or mixtures thereof.
- further structural units would be present to a minor extent, for example in an amount smaller than 5 wt.-% based on the total weight of the polyester of the invention.
- alkyl and alkenyl groups R 1 in the one or more terminal groups of the formula (lll-a) are, for example, linear or branched heptyl, octyl (e.g. capryl), nonyl, decyl, undecyl, dodecyl, tridecyl (e.g.
- the groups R 1 in the one or more terminal groups of the formula (lll-a) may also be mixtures which have been derived or obtained from natural sources and comprise one or more alkyl and/or one or more alkenyl groups and in case these mixtures comprise one or more alkenyl groups, they may also be partially or totally hydrogenated. Examples of such mixtures are cocoyl, partially or totally hydrogenated variants of cocoyl, talloyl or partially or totally hydrogenated variants of talloyl.
- R 1 preferably is selected from the group consisting of lauryl, myristyl and mixtures thereof.
- R 1 in the one or more terminal groups of the formula (lll-a) is selected from the group consisting of linear or branched C10-C15 alkyl (such as lauryl, myristyl or isotridecyl), cocoyl, partially or totally hydrogenated variants of cocoyl, talloyl, partially or totally hydrogenated variants of talloyl and mixtures thereof, more preferably is selected from the group consisting of linear or branched, preferably linear, C10-C15 alkyl, talloyl, partially or totally hydrogenated variants of talloyl and mixtures thereof, even more preferably is selected from the group consisting of linear or branched, preferably linear, C10-C15 alkyl, partially or totally hydrogenated variants of talloyl and mixtures thereof and particularly preferably is selected from the group consisting of lauryl, myristyl, partially or totally hydrogenated variants of talloyl and mixtures thereof.
- C10-C15 alkyl such as lauryl, myr
- R 1 is a linear or branched, preferably a linear, alkyl group comprising from 7 to 30 carbon atoms or mixtures thereof, more preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or mixtures thereof, even more preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or mixtures thereof, and particularly preferably is selected from the group consisting of lauryl, myristyl and mixtures thereof.
- [0(CmH2m)] groups for example [0(C2H4)], [0(C3H6)] and [0(04Hd)] groups, exist in a terminal group of the formula (lll-a), they may be arranged blockwise, alternating, periodically and/or statistically, preferably blockwise and/or statistically. This means that in a terminal group of the formula (lll-a), the [0(CmH2m)] groups, and e.g.
- the groups [0(C2H4)], [0(C3H6)] and [0(04Hd)] may be arranged, for example, in a purely statistically or blockwise form but may also be arranged in a form which could be considered as both statistical and blockwise, e.g. small blocks of [(OC2H4)] and [0(C3H6)] arranged in a statistical manner, or in a form wherein adjacent instances of statistical and blockwise arrangements of the groups [0(C2H4)], [0(C3H6)j and [0(C4He)] exist.
- any of the groups [0(CmH2m)], e.g. any of the groups [0(C2H4)], [0(C3H6)j and [0(C4He)], can be linked to R 1 - and -0 in a terminal group of the formula (lll-a).
- both, R 1 - and -O in a terminal group of the formula (lll-a), may be connected to a [0(C2H4)j group, they may both be connected to a [0(03Hd)] group, they may both be connected to a [0(C4He)] group or they may be connected to different groups selected from [0(C2H4)j, [0(03Hd)] and [0(C 4 H 8 )].
- one molecule of the polyesters of the invention comprises two or more terminal groups of the formula (lll-a) the definition of R 1 , R 2 and “a” may vary between those terminal groups.
- R 1 is a linear or branched, preferably a linear, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, and preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 18 carbon atoms or mixtures thereof, and “a” is, based on a molar average, a number from 60 to 150.
- R 1 is a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 15 carbon atoms, or mixtures thereof, and “a” is, based on a molar average, a number from 1 to 200, preferably from 10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150.
- R 1 preferably is a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or mixtures thereof and “a” is, based on a molar average, a number from 1 to 200, preferably from 10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150, and more preferably, R 1 is selected from the group consisting of lauryl, myristyl and mixtures thereof and “a” is, based on a molar average, a number from 1 to 200, preferably from 10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150.
- the polyesters comprise one or more polyalkyleneglycol-derived structural units of the formula (IV-a) or mixtures thereof, wherein f is, based on a molar average, a number from 2 to 200, preferably from
- R 3 is a linear or branched alkylene group (Cnhten) with n being a number from 2 to 10 or mixtures thereof, preferably with n being a number from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (C3H6), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (C3H6) and mixtures thereof, and particularly preferably is (C2H4).
- Cnhten linear or branched alkylene group (Cnhten) with n being a number from 2 to 10 or mixtures thereof, preferably with n being a number from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (C3H6), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (C3H6) and mixtures thereof, and particularly preferably is (C2H4).
- [(CnH2n)0] groups for example [(C2H4)0], [(C3H6)0] and [(C4He)0] groups, exist in a structural unit of the formula (IV-a), they may be arranged blockwise, alternating, periodically and/or statistically, preferably blockwise and/or statistically. This means that in a structural unit of the formula (IV-a), the [(CnH2n)0] groups, and e.g.
- the groups [(C2H4)0], [(C3H6)0] and [(C4He)0] may be arranged, for example, in a purely statistically or blockwise form but may also be arranged in a form which could be considered as both statistical and blockwise, e.g. small blocks of [(C2H4)0] and [(C3H6)0] arranged in a statistical manner, or in a form wherein adjacent instances of statistical and blockwise arrangements of the groups [(C2H4)0], [(C3H6)0] and [(C4He)0] exist.
- any of the groups [(CnH2n)0], e.g. any of the groups [(C2H4)0], [(C3H6)0] and [(C4He)0] can form an end group of the structure element -[R 3 -0]f-
- the two end groups of the structure element -[R 3 -0]f- in a structural unit of the formula (IV-a) may be formed by [(C2H4)0] groups, may be formed by [(C3H6)0] groups, may be formed by [(C4He)0] groups or may be formed by different groups selected from [(C2H4)0], [(C3H6)0] and [(C4He)0].
- one molecule of the polyesters of the invention comprises two or more structural units of the formula (IV-a) the definition of R 3 and “f” may vary between those structural units.
- the amount of the one or more terminal groups of the formula (lll-a) or mixtures thereof preferably is at least 40 wt.-%, more preferably is from 40 to 90 wt.-% and even more preferably is from 50 to 90 wt.-%, in each case based on the total weight of the polyester.
- the combined amount of the one or more structural units of the formula (I), and the one or more structural units of the formula (II), and the one or more terminal groups of the formula (lll-a) or mixtures thereof, and, if present, the one or more polyalkyleneglycol-derived structural units of the formula (IV-a) or mixtures thereof preferably is at least 50 wt.-%, more preferably is at least 60 wt.-% and even more preferably is at least 70 wt.-%, in each case based on the total weight of the polyester.
- the weight average molecular weight (Mw) of the inventive polyesters is from 5000 to 20000 g/mol.
- the weight average molecular weight (Mw) of the inventive polyesters may be determined by GPC analysis, preferably as detailed in the following: 10 m I of sample is injected onto a PSS Suprema column of dimensions 300 x 8 mm with porosity 30 A and particle size 10 pm. The detection is monitored at 235 nm on a multiple wavelength detector.
- the employed eluent is 1.25 g/l of disodium hydrogen phosphate in a 45 / 55 % (v/v) water / acetonitrile mixture. Separations are conducted at a flow rate of 0.8 ml/minute. Quantification is performed by externally calibrating standard samples of different molecular weight polyethylene glycols.
- the number of structural units of the formula (I) in the polyesters of the invention is, based on a molar average, from 2 to 60, more preferably from 2 to 40, even more preferably from 2 to 30, particularly preferably from 2 to 20 and especially preferably from 5 to 20.
- the polyesters of the invention comprise one or more terminal groups of the formula (lll-a) or mixtures thereof.
- the inventive polyesters may comprise further terminal groups, preferably selected from the group consisting of -OH, -OCH2CH(CH3)OH, -0CH(CH3)CH20H and mixtures thereof.
- the polyesters of the invention may also comprise terminal groups of the formula -0-[R 3 -0]f-H wherein R 3 and “f” have the meaning given above.
- the polyester molecules of the invention comprise two or more terminal groups of the formula (lll-a) or mixtures thereof. Even more preferably, all terminal groups of the polyester molecules of the invention are terminal groups of the formula (lll-a) or mixtures thereof.
- the inventive polyesters consist of a1 ) one or more structural units of the formula (I) and a2) one or more structural units of the formula (II) and a3) one or more terminal groups of the formula (lll-a) or mixtures thereof.
- the inventive polyesters consist of b1 ) one or more structural units of the formula (I) and b2) one or more structural units of the formula (II) and b3) one or more terminal groups of the formula (lll-a) or mixtures thereof, and b4) one or more polyalkyleneglycol-derived structural units of the formula (IV-a) or mixtures thereof.
- polyesters of the invention typically a two-stage process is used of either direct esterification of diacids and diols or transesterification of diesters and diols, followed by a polycondensation reaction under reduced pressure.
- a further subject matter of the invention is a process for the preparation of the inventive polyesters, comprising the steps of: heating one or more substances of the formula Q1-OOC-C6H4-COO-Q2, wherein Q1 and Q2, independently of one another, are selected from the group consisting of H and (Ci-C4)-alkyl and preferably are CFta, and 1 ,2-propyleneglycol, and one or more substances of the formula R 1 -[0-R 2 ] a -0H or mixtures thereof, wherein R 1 , R 2 and “a” have the meaning given above, with the addition of a catalyst, to temperatures of from 160 to 220°C, preferably beginning at atmospheric pressure, and then continuing the reaction under reduced pressure at temperatures of from 160 to 240°C.
- Reduced pressure preferably means a pressure of from 0.1 to 900 mbar and more preferably a pressure of from 0.5 to 500 mbar.
- Typical transesterification and condensation catalysts known in the art can be used for the inventive process for the preparation of the inventive polyesters, such as antimony, germanium and titanium-based catalysts.
- tetraisopropyl orthotitanate (IPT) and sodium acetate (NaOAc) are used as the catalyst system in the inventive process for the preparation of the polyesters of the invention.
- polyesters of the invention comprising one or more polyalkyleneglycol-derived structural units of the formula -0-[R 3 -0]f- (IV-a) or mixtures thereof
- the respective one or more polyalkyleneglycols of the formula HO-[ R 3 -0]f-H or mixtures thereof may be employed in the inventive process for the preparation of the polyesters of the invention.
- the inventive polyesters may advantageously be used as soil release agents.
- a further subject matter of the invention therefore is the use of one or more polyesters of the invention as soil release agents.
- soil release agent as used herein means an agent that enhances soil removal during laundering by modifying the surface of the fabric that is laundered, preferably by increasing surface polarity.
- the inventive polyesters may advantageously be used in detergent compositions.
- a further subject matter of the invention therefore is the use of one or more polyesters of the invention in detergent compositions.
- a further subject matter of the invention is detergent compositions comprising Z1 ) one or more polyesters of the invention and Z2) one or more surfactants.
- the inventive detergent compositions are preferably laundry detergent compositions.
- the detergent compositions of the invention comprise the one or more polyesters of component Z1 ) preferably in an amount of at least 0.1 wt.-%, more preferably in an amount from 0.1 to 10 wt.-%, even more preferably in amount from 0.2 to 5 wt.-% and particularly preferably in an amount from 0.2 to 3 wt.-%, in each case based on the total weight of the detergent composition.
- the detergent compositions of the invention comprise one or more surfactants as component Z2).
- Surfactants assist in removing soil from textile materials and also assist in main taining removed soil in solution or suspension in the wash liquor.
- the one or more surfactants of component Z2) of the detergent compositions of the invention are selected from the group consisting of anionic, nonionic, cationic and zwitterionic surfactants, and more preferably from the group consisting of anionic, nonionic and zwitterionic surfactants.
- Suitable anionic surfactants that may be used are any of the conventional anionic surfactant types typically used in detergent products. These include alkyl sulfonates, alkyl ether sulfates, alkyl sulfates, alkyl ester sulfonates and soaps. Preferred anionic surfactants are alkylbenzene sulfonates, alkyl ether sulfates, alkyl sulfates and soaps.
- Preferred alkyl sulfonates are alkylbenzene sulfonates, particularly linear alkyl benzene sulfonates (LAS) having an alkyl chain length of Cs-C-is.
- Possible counter ions for concentrated alkaline liquids are ammonium ions, e.g. those generated by the neutralization of alkylbenzene sulfonic acid with one or more ethanolamines, for example monoethanolamine (MEA) and triethanolamine (TEA), or alternatively, alkali metals, e.g. those arising from the neutralization of alkylbenzene sulfonic acid with alkali hydroxides.
- the linear alkyl benzene sulfonate surfactants may be LAS with an alkyl chain length of preferably from 8 to 15 and more preferably from 12 to 14.
- the neutralization of the acid may be performed before addition to the detergent compositions of the invention or during the process of formulating the detergent compositions of the invention through excess addition of neutralizing agent.
- alkyl ether sulfates are alkyl polyethoxylate sulfate anionic surfactants of the formula
- R 4 is a saturated or unsaturated alkyl chain having preferably from 10 to 22 carbon atoms, and more preferably from 12 to 16 carbon atoms,
- M + is a cation which makes the compound water-soluble, preferably an ammonium cation, a substituted ammonium cation, an alkali metal cation, or other material chosen from the list of buffers, and y averages preferably from 1 to 15, more preferably from 1 to 3 and even more preferably is 3.
- A alkyl sulfates
- R 5 is a linear or branched alkyl chain having preferably from 8 to 24 carbon atoms, and more preferably from 12 to 18 carbon atoms
- M + is a cation which makes the compound water-soluble, preferably an ammonium cation, a substituted ammonium cation, an alkali metal cation, or other material chosen from the list of buffers.
- Soaps are preferably fatty acids and more preferably linear saturated or unsatured fatty acids having from 10 to 18 carbon atoms.
- Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamides) such as N-methyl glucamides. Mixtures of nonionic surfactant may be used.
- the detergent compositions of the invention contain preferably from 0.2 to 40 wt.-% and more preferably from 1 to 20 wt.-% of a nonionic surfactant, such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides").
- a nonionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”).
- the detergent compositions of the invention may comprise up to 10 wt.-% of a zwitterionic surfactant, e.g. amine oxide or betaine.
- a zwitterionic surfactant e.g. amine oxide or betaine.
- Typical amine oxides used are of the formula
- R 6 is a long chain moiety and each CH2R 7 are short chain moieties
- R 7 is preferably selected from the group consisting of H, CH3 and -CH2OH.
- R 6 is a primary or branched hydrocarbyl moiety with a chain length of from 8 to 18, which can be saturated or unsaturated.
- R 6 is a primary alkyl moiety with a chain length of 8 to 18 carbon atoms.
- Preferred amine oxides have compositions wherein R 6 is a Cs-C-is alkyl and R 7 is H. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
- a preferred amine oxide material is lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO.
- Betaines may be alkyldimethyl betaines or alkylamido betaines, wherein the alkyl groups have C12-18 chains.
- the one or more surfactants of component Z2) of the detergent compositions of the invention are selected from the group consisting of linear alkyl benzene sulfonates, alkyl ether sulfates, alkyl sulfates, soaps, nonionic surfactants, amine oxides and betaines, and preferably the one or more surfactants of component Z2) of the detergent compositions of the invention are selected from the group consisting of linear alkyl benzene sulfonates, alkyl ether sulfates, alkyl sulfates, soaps and nonionic surfactants.
- surfactants than the preferred LAS, AES, AS, soaps and nonionic surfactants may be added to the mixture of detersive surfactants.
- the detergent compositions of the invention comprise the one or more surfactants of component Z2) preferably in an amount of at least 3 wt.-%, more preferably in an amount from 3 to 65 wt.-%, even more preferably in an amount from 4 to 60 wt.-% and particularly preferably in an amount from 5 to 55 wt.-%, in each case based on the total weight of the detergent composition.
- the detergent compositions of the invention may comprise one or more optional ingredients, e.g. they may comprise conventional ingredients commonly used in detergent compositions, especially laundry detergent compositions.
- optional ingredients include, but are not limited to builders, bleaching agents, bleach active compounds, bleach activators, bleach catalysts, photobleaches, dye transfer inhibitors, colour protection agents, anti-redeposition agents, dispersing agents, fabric softening and antistatic agents, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, malodour reducers, preservatives, disinfecting agents, hydrotropes, fibre lubricants, anti-shrinkage agents, buffers, fragrances, processing aids, colorants, dyes, pigments, anti-corrosion agents, fillers, stabilizers and other conventional ingredients for detergent compositions such as washing or laundry detergent compositions.
- This second polymer is preferably a polyalkoxylated polyethyleneimine (EPEI).
- EPEI polyalkoxylated polyethyleneimine
- Polyethylene imines are materials composed of ethylene imine units -CFI2CFI2NFI- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.
- the detergent compositions of the invention may comprise other polymeric materials, for example: dye transfer inhibition polymers, anti-redeposition polymers and cotton soil release polymers, especially those based on modified cellulosic materials.
- the detergent compositions of the invention may further comprise a polymer of polyethylene glycol and vinyl acetate, for example the lightly grafted copolymers described in WO 2007/138054.
- amphiphilic graft polymers based on water soluble polyalkylene oxides as graft base and side chains formed by polymerisation of a vinyl ester component have the ability to enable reduction of surfactant levels whilst maintaining high levels of oily soil removal.
- a hydrotrope is a solvent that is neither water nor conventional surfactant that aids the solubilisation of the surfactants and other components, especially polymer and sequestrant, in the liquid to render it isotropic.
- suitable hydrotropes there may be mentioned as preferred: monopropylene glycol (MPG), glycerol, sodium cumene sulfonate, ethanol, other glycols, e.g. dipropylene glycol, diethers and urea. MPG and glycerol are preferred hydrotropes.
- one or more enzymes selected from protease, mannanase, pectate lyase, cutinase, lipase, amylase, and cellulase may be present in the detergent compositions of the invention. Less preferred additional enzymes may be selected from esterase, peroxidase and oxidase. The enzymes are preferably present with corresponding enzyme stabilizers.
- the total enzyme content in the detergent compositions of the invention is preferably from 0 to 5 wt.-%, more preferably from 0.2 to 4 wt.-% and even more preferably from 0.4 to 2 wt.-%, in each case based on the total weight of the detergent composition.
- Sequestrants are preferably included.
- Preferred sequestrants include organic phosphonates, alkanehydroxy phosphonates and carboxylates available under the DEQUEST trademark from Thermphos.
- the preferred sequestrant level is less than 10 wt.-% and preferably less than 5 wt.-% of the detergent composition of the invention.
- a particularly preferred sequestrant is HEDP (1-Hydroxyethylidene-1 ,1 ,- diphosphonic acid).
- DTPMP diethylenetriamine penta(methylene phosphonic acid)
- Heptasodium DTPMP diethylenetriamine penta(methylene phosphonic acid)
- buffers are one or more ethanolamines, e.g. monoethanolamine (MEA) or triethanolamine (TEA). They are preferably used in the detergent compositions of the invention at levels of from 1 to 15 wt.-%, based on the total weight of the detergent composition.
- Other suitable amino alcohol buffer materials may be selected from the group consisting of compounds having a molecular weight above 61 g/mol, which includes MEA.
- Suitable materials also include, in addition to the already mentioned materials: monoisopropanolamine, diisopropanolamine, triisopropanolamine, monoamino hexanol, 2-[(2-methoxyethyl) methylamino]- ethanol, propanolamine, N-methylethanolamine, diethanolamine, monobutanolamine, isobutanolamine, monopentanolamine, 1-amino-3-(2- methoxyethoxy)-2-propanol, 2-methyl-4-(methylamino)-2-butanol and mixtures thereof.
- amino ethanol buffers are alkali hydroxides such as sodium hydroxide or potassium hydroxide.
- Further washing and cleaning ingredients which may be present in the detergent compositions of the invention include inorganic and/or organic builders in order to reduce the degree of hardness of the water. These builders may be present in the detergent compositions of the invention in amounts of from about 5 to about 80 wt.-%, based on the total weight of the detergent compositions.
- Inorganic builders include, for example, alkali metal, ammonium and alkanolammonium salts of polyphosphates, silicates, carbonates, sulfates and aluminosilicates.
- Suitable organic builders include polycarboxyl compounds, such as, for example, ether polycarboxylates, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 ,3,5-trihydroxybenzene-2,4,6- trisulfonic acid and carboxymethyloxysuccinic acid, the alkali metal, ammonium and substituted ammonium salts of polyacetic acids, such as, for example, ethylenediaminetetraacetic acid and nitrilotriacetic acid, and also polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1 ,3, 5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
- polycarboxyl compounds such as, for example, ether polycarboxylates, ether hydroxypolycarboxylates, copolymers of male
- citrates for example citric acid and its soluble salts, in particular the sodium salt
- polycarboxylic acid builders which can also be used in granulated compositions, in particular together with zeolites and/or sheet silicates.
- the detergent compositions of the invention may additionally contain viscosity modifiers, foam boosting agents, preservatives (e.g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids.
- the detergent compositions of the invention may further comprise pearlisers and/or opacifiers or other visual cues and shading dye.
- the detergent compositions of the invention may be in solid or in liquid form, including a gel form.
- the detergent compositions of the invention may be packaged as unit doses in a polymeric film soluble in the wash water.
- the detergent compositions of the invention may be supplied in multidose plastics packs with a top or bottom closure.
- a dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.
- the polyesters of the invention may be used in substance, i.e. as granules, but may also be provided as solutions or dispersions. The latter two exhibit beneficial handling properties and are more easily dosed.
- the solutions or dispersions comprise the polyesters of the invention in an amount from 25 to 70 weight-% based on the total weight of the solution or dispersion.
- Suitable solvents for such solutions or dispersions are for example water, ethanol, propanol, butanol, ethylene glycol, 1,2-propylene glycol, 1 ,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, butyl glycol, butyl diglycol and butyl polyglycol.
- These solvents are preferably used in an amount from 25 to 75 wt.-% and more preferably in an amount from 30 to 75 wt.-%, in each case based on the total weight of the solution or dispersion.
- the inventive solutions or dispersions comprise water and a second solvent different from water and selected from the group above.
- a further subject matter of the invention is solutions or dispersions comprising one or more polyesters of the invention, preferably in an amount from 25 to 70 wt.-%, based on the total weight of the solution or dispersion, and one or more solvents selected from the group consisting of water, ethanol, propanol, butanol, ethylene glycol, 1,2-propylene glycol, 1 ,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1 ,4-butylene glycol, butyl glycol, butyl diglycol and butyl polyglycol, preferably in an amount from 25 to 75 wt.-% and more preferably in an amount from 30 to 75 wt.-%, in each case based on the total weight of the solution or dispersion.
- the inventive solutions or dispersions comprise water and a second solvent different from water and selected from the group above.
- inventive solutions or dispersions are liquid and comprise the one or more polyesters of the invention in a high concentration. They may e.g. represent high concentrated liquid handling forms of the inventive polyesters and may be used for the preparation of inventive detergent compositions to be used by end-consumers. These inventive solutions or dispersions comprising the one or more polyesters of the invention in a high concentration nevertheless possess an advantageous low viscosity in the sense that this viscosity causes, for example, no issues on pumpability or dosage consistency during the preparation of the inventive detergent compositions to be used by end-consumers.
- the groups (C2H4) in the terminal groups of the formula (lll-a) or in the structural units of the formula (IV-a) preferably are of the formula -CH2-CH2-.
- the groups (C3H6) in the terminal groups of the formula (lll-a) or in the structural units of the formula (IV-a) preferably are of the formula -CH(CH3)-CH2- or -CH2- CH(CH3)-, i.e. of the formula:
- the groups (C4H8) in the terminal groups of the formula (lll-a) or in the structural units of the formula (IV-a) preferably are of the formula -CH(CH3)-CH(CH3)-, i.e. of the formula:
- terminal groups or structural units of the formulae (II), (lll-a) or (IV-a) may be linked directly to structural units of the formula (I) resulting in ester groups.
- polyesters of the invention are typically prepared by polycondensation processes. This leads to statistically determined mixtures of polyesters in which a mixture of molecular species with a distribution around a molar average is obtained.
- the terminal group of the formula (lll-a) is linked to an acyl group derived from a dicarboxylic acid, preferably to the structural unit of the formula (I), which - in the case of structural unit of the formula (I) and terminal group of the formula (lll-a) - results in the following structural entity:
- Tallow-80EO Tallow alcohol (C16/18, C18 rich, saturated (hydrogenated)) ethoxylate with 80 EO (Genapol ® T 800, Clariant)
- Lauryl-80EO Lauryl alcohol (C12/14, C12 rich) ethoxylate with 80 EO
- IsotridecyMOOEO Isotridecyl alcohol (C11-C14 iso alcohol, C13 rich) ethoxylate with 100 EO
- the polyester synthesis is carried out by the reaction of dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG) and one or more poly(alkyleneglycol)monoalkylethers or one or more poly(alkyleneglycol)monoalkenylethers or mixtures thereof (collectively “Cap”), using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as the catalyst system.
- DMT dimethyl terephthalate
- PG 1 ,2-propylene glycol
- Cap poly(alkyleneglycol)monoalkylethers or one or more poly(alkyleneglycol)monoalkenylethers or mixtures thereof
- NaOAc sodium acetate
- IPT tetraisopropyl orthotitanate
- methanol is released from the reaction and is distilled out of the system (distillation temperature ⁇ 55°C). After 2 hours at 210°C nitrogen is switched off and the pressure is reduced to 400 mbar over 3 hours. Subsequently, the mixture is heated up to 230°C. At 230°C, the pressure is reduced to 1 mbar over 160 minutes. Once the polycondensation reaction has started, 1,2-propylene glycol is distilled out of the system. The mixture is stirred for 4 hours at 230°C and a pressure of 1 mbar. The reaction mixture is cooled down to 140 - 150°C. Vacuum is released with nitrogen and the molten polymer is transferred out of the reactor.
- Inventive polyester examples 2 to 14 are synthesized according to the general procedure as described above for inventive polyester example 1 with monomer type and dosage described below (see Table 1).
- Example 2 Compositions containing polyesters and their viscosity
- a series of exemplary liquid laundry detergent compositions containing no polyester (reference composition A), containing a comparative polyester (comparative composition B) or containing inventive polyester (inventive compositions C-M) were prepared according to Table 2.
- LAS is C-12-14 linear alkylbenzene sulfonate, sodium salt
- SLES 2EO is sodium lauryl ether sulfate with 2 moles EO (Genapol ®
- Nl 7EO is C-12-15 alcohol ethoxylate 7EO nonionic (Genapol ®
- LA070, Clariant Fatty Acid is a C12-18 stripped palm kernel fatty acid SRP is a polyester prepared according to examples from
- Texcare ® SRN 260 is a nonionic soil release polymer (Clariant)
- Table 2 Liquid laundry detergent compositions for performance testing a.m. active matter
- the viscosities of the compositions of Table 2 were determined using a Malvern Kinexus equipped with a CP 4 40 mm, at a temperature of 25 °C and at a shear rate of 200 s 1 and rounded to the nearest 5 mPas. The appearance of the compositions was determined visually. The results are summarized in Table 3.
- Detergent compositions of Example 2 were tested for their soil release performance according to the “Dirty-Motor ON” Test (DMO-Test) using a Lini Apparatus under the following conditions (see Table 4).
- DMO-Test Dynamic Motor ON Test
- test fabric white polyester standard swatches (WFK 30A from WFK Testgewebe GmbFI) were used. The fabrics were prewashed three times with the liquid detergent compositions. The swatches were then rinsed, dried and soiled with 25 pi of dirty motor oil. After 1 hour the soiled fabrics were washed again with the same stored laundry detergent compositions used in the pre-washing step. After rinsing and drying the washed swatches, a measurement of the remission of the stained fabric at 457 nm was made using a spectrophotometer (Datacolor 650).
- composition A The soil release performance is shown as an improvement in soil removal of the swatches washed with a composition containing an inventive polyester as additive compared with the same composition containing no additive (Composition A)
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Abstract
Polyesters are described comprising one or more structural units of the formula (I) and one or more structural units of the formula (II) and one or more terminal groups of the formula (III-a) or mixtures thereof (III-a) wherein R1 is a linear or branched alkyl group comprising from 7 to 30 carbon atoms or a linear or branched alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, and R2 is a linear or branched alkylene group (CmH2m) with m being a number from 2 to 10 or mixtures thereof. The polyesters are particularly suited to be used as soil release agents.
Description
Soil release polyesters for use in detergent compositions
The invention relates to specific polyesters, a process for their preparation, their use as soil release agents, their use in detergent compositions, detergent compositions comprising the polyesters and surfactants and solutions or dispersions comprising the polyesters.
Polyester containing fabrics can be surface modified to increase the hydrophilicity of the fabric, which can improve soil removal. Such surface modification can be achieved through direct treatment of the fabric, as outlined for example in GB 1 ,088,984, or more preferably through deposition of a surface modifying polymer in a washing process, as disclosed for example in US 3,962,152. The renewable soil release finish imparted through washing ensures the continuous protection of the fiber from oily stains.
The polymers used in these processes typically consist of a polyester midblock with either one or two endblocks of polyethylene glycol, as further outlined in US 3,959,230 and US 3,893,929.
The inclusion of anionic moieties in the polymer structure is known to improve the efficacy of these soil release polymers and in particular, improve their anti redeposition properties. For example, DE 102007013217 and EP 1 966273 disclose anionic polyesters that may be used as soil release agents in laundry detergents. Such anionic soil release polymers are particularly well suited for use in powder detergents due to their handling properties and compatibility with the detergent composition.
The use of nonionic soil release agents in liquid laundry detergents is well known in the art. GB 1 ,466,639, US 4, 132,680, US 4,702,857, EP 0 199403,
US 4,711 ,730, US 4,713,194 and US 4,759,876 disclose aqueous detergent compositions containing soil release polymers.
A typical property of existing soil release polymers described in the prior art is their tendency to significantly reduce the viscosity of detergent compositions. While comparatively low viscosities of concentrates to be used for the preparation of detergent compositions are advantageous for their handling, e.g. with regard to pumpability or dosage consistency, end-consumers tend to correlate higher viscosities of detergent compositions with better performance. To compensate for the reduction in viscosity by the addition of such soil release polymers, the formulator must add additional components to the detergent composition to regain this viscosity. The latter is non-ideal as this can bring additional costs and effort. Moreover, the use of additional materials is not preferred from an environmental aspect.
Therefore, it was an object of the present invention to provide new polyesters which possess or lead to advantageous soil release and viscosity properties and preferably do not reduce or even increase the viscosity of detergent compositions.
Surprisingly, it has been found that this problem is solved by polyesters comprising one or more structural units of the formula (I)
and one or more structural units of the formula (II)
and one or more terminal groups of the formula (lll-a) or mixtures thereof
(lll-a)
wherein
R1 is a linear or branched, preferably a linear, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 18 carbon atoms or mixtures thereof, and more preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 15 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, preferably from 10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150, and
R2 is a linear or branched alkylene group (Cmhtem) with m being a number from 2 to 10 or mixtures thereof, preferably with m being a number from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (C3H6), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (C3H6) and mixtures thereof, and particularly preferably is (C2H4).
Therefore, a subject matter of the present invention is polyesters comprising one or more structural units of the formula (I)
and one or more structural units of the formula (II)
and one or more terminal groups of the formula (lll-a) or mixtures thereof
(lll-a)
wherein
R1 is a linear or branched, preferably a linear, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 18 carbon atoms or mixtures thereof, and more preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 15 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, preferably from
10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150, and
R2 is a linear or branched alkylene group (Cmhtem) with m being a number from 2 to 10 or mixtures thereof, preferably with m being a number from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (C3H6), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (C3H6) and mixtures thereof, and particularly preferably is (C2H4).
The polyesters of the invention possess or lead to advantageous soil release and viscosity properties and preferably do not reduce or even increase the viscosity of detergent compositions. The inventive polyesters additionally e.g. show beneficial compatibility with liquid detergent compositions, detergency enhancement, advantageous hydrolysis stability, and beneficial anti-greying effects.
EP 0442 101 discloses polyesters containing nonionic surfactants in a condensed form, their preparation and their use in detergents.
WO 97/30141 discloses polyetherestercarbonate as dirt dissolving polymers in washing and textile adjuvants.
WO 95/32232 discloses soil release polymers that effectively remove greasy soils.
The one or more structural units of the formula (I) of the polyesters of the invention are derived from terephthalic acid or its salts or its dialkyl esters, preferably its (Ci-C4)-dialkyl esters and more preferably its dimethyl ester, or mixtures thereof.
In addition to the one or more structural units of the formula (I) further structural units derived from other di- or polycarboxylic acids or their salts or their (di)alkylesters can be used in the polyesters of the invention, such as, phthalic acid, isophthalic acid, 5-sulfoisophthalic acid, 3-sulfophthalic acid, 4-sulfophthalic acid, naphthalene-1 ,4-dicarboxylic acid, naphthalene-2, 6, -dicarboxylic acid, tetrahydrophthalic acid, trimellitic acid, diphenoxyethane-4, 4' -dicarboxylic acid, diphenyl-4, 4'-dicarboxylic acid, 2,5-furandicarboxylic acid, adipic acid, sebacic acid, decan-1 ,10-dicarboxylic acid, fumaric acid, succinic acid,
1.4-cyclohexanedicarboxylic acid, cyclohexanediacetic acid, glutaric acid, azelaic acid, or their salts or their (di)alkyl esters, preferably their (Ci-C4)-(di)alkyl esters and more preferably their (di)methyl esters, or mixtures thereof. Typically, such further structural units derived from other di- or polycarboxyl ic acids or their salts or their (di)alkylesters would be present to a minor extent, for example in an amount smaller than 5 wt.-%, based on the total weight of the polyester of the invention.
The one or more structural units of the formula (II) of the polyesters of the invention are derived from 1,2-propyleneglycol.
In addition to the one or more structural units of the formula (II), further structural units derived from other glycols can be used in the polyesters of the invention, such as, ethyleneglycol, 1,3-propyleneglycol, 2-methyl-1 ,3-propanediol,
1.4-butanediol, 1 ,3-butanediol, 2,3-butanediol, 1,2-butanediol, 2, 2-dimethyl-1 ,3- propanediol, 1,2-pentanediol, 1 ,5-pentanediol, 1 ,2-hexanediol, 1 ,6-hexanediol or mixtures thereof. Typically, such further structural units would be present to a minor extent, for example in an amount smaller than 5 wt.-% based on the total weight of the polyester of the invention.
In addition, further structural units derived from triols or tetraols can be used in the polyesters of the invention, such as, glycerol, pentaerythritol or mixtures thereof. Typically, such further structural units would be present to a minor extent, for example in an amount smaller than 5 wt.-% based on the total weight of the polyester of the invention.
Examples of the alkyl and alkenyl groups R1 in the one or more terminal groups of the formula (lll-a) are, for example, linear or branched heptyl, octyl (e.g. capryl), nonyl, decyl, undecyl, dodecyl, tridecyl (e.g. isotridecyl), tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetraicosyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, octadecadienyl, octadecatrienyl, eicosenyl,
eicosadienyl, eicosatetraenyl, docosenyl, docosahexaenyl, tetracosenyl, or mixtures thereof.
The groups R1 in the one or more terminal groups of the formula (lll-a) may also be mixtures which have been derived or obtained from natural sources and comprise one or more alkyl and/or one or more alkenyl groups and in case these mixtures comprise one or more alkenyl groups, they may also be partially or totally hydrogenated. Examples of such mixtures are cocoyl, partially or totally hydrogenated variants of cocoyl, talloyl or partially or totally hydrogenated variants of talloyl.
Among the linear alkyl groups comprising from 10 to 15 carbon atoms or mixtures thereof in the definition of R1, which also can be described as linear C10-C15 alkyl or mixtures thereof, R1 preferably is selected from the group consisting of lauryl, myristyl and mixtures thereof.
In a preferred embodiment of the invention, R1 in the one or more terminal groups of the formula (lll-a) is selected from the group consisting of linear or branched C10-C15 alkyl (such as lauryl, myristyl or isotridecyl), cocoyl, partially or totally hydrogenated variants of cocoyl, talloyl, partially or totally hydrogenated variants of talloyl and mixtures thereof, more preferably is selected from the group consisting of linear or branched, preferably linear, C10-C15 alkyl, talloyl, partially or totally hydrogenated variants of talloyl and mixtures thereof, even more preferably is selected from the group consisting of linear or branched, preferably linear, C10-C15 alkyl, partially or totally hydrogenated variants of talloyl and mixtures thereof and particularly preferably is selected from the group consisting of lauryl, myristyl, partially or totally hydrogenated variants of talloyl and mixtures thereof.
In a further preferred embodiment of the invention, R1 is a linear or branched, preferably a linear, alkyl group comprising from 7 to 30 carbon atoms or mixtures thereof, more preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or mixtures thereof, even more preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to
15 carbon atoms or mixtures thereof, and particularly preferably is selected from the group consisting of lauryl, myristyl and mixtures thereof.
In the case that at least two different types of [0(CmH2m)] groups, for example [0(C2H4)], [0(C3H6)] and [0(04Hd)] groups, exist in a terminal group of the formula (lll-a), they may be arranged blockwise, alternating, periodically and/or statistically, preferably blockwise and/or statistically. This means that in a terminal group of the formula (lll-a), the [0(CmH2m)] groups, and e.g. the groups [0(C2H4)], [0(C3H6)] and [0(04Hd)], may be arranged, for example, in a purely statistically or blockwise form but may also be arranged in a form which could be considered as both statistical and blockwise, e.g. small blocks of [(OC2H4)] and [0(C3H6)] arranged in a statistical manner, or in a form wherein adjacent instances of statistical and blockwise arrangements of the groups [0(C2H4)], [0(C3H6)j and [0(C4He)] exist.
Any of the groups [0(CmH2m)], e.g. any of the groups [0(C2H4)], [0(C3H6)j and [0(C4He)], can be linked to R1- and -0 in a terminal group of the formula (lll-a). This means, for example, that both, R1- and -O in a terminal group of the formula (lll-a), may be connected to a [0(C2H4)j group, they may both be connected to a [0(03Hd)] group, they may both be connected to a [0(C4He)] group or they may be connected to different groups selected from [0(C2H4)j, [0(03Hd)] and [0(C4H8)].
In the case that one molecule of the polyesters of the invention comprises two or more terminal groups of the formula (lll-a) the definition of R1, R2 and “a” may vary between those terminal groups.
In a preferred embodiment of the invention R1 is a linear or branched, preferably a linear, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, and preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double
bonds and from 10 to 18 carbon atoms or mixtures thereof, and “a” is, based on a molar average, a number from 60 to 150.
In a further preferred embodiment of the invention, R1 is a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 15 carbon atoms, or mixtures thereof, and “a” is, based on a molar average, a number from 1 to 200, preferably from 10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150. In this preferred embodiment of the invention, R1 preferably is a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or mixtures thereof and “a” is, based on a molar average, a number from 1 to 200, preferably from 10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150, and more preferably, R1 is selected from the group consisting of lauryl, myristyl and mixtures thereof and “a” is, based on a molar average, a number from 1 to 200, preferably from 10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150.
In a preferred embodiment of the invention the polyesters comprise one or more polyalkyleneglycol-derived structural units of the formula (IV-a)
or mixtures thereof, wherein f is, based on a molar average, a number from 2 to 200, preferably from
10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150, and
R3 is a linear or branched alkylene group (Cnhten) with n being a number from 2 to 10 or mixtures thereof, preferably with n being a number from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (C3H6), (C4H8) and mixtures thereof, even more preferably is
selected from the group consisting of (C2H4), (C3H6) and mixtures thereof, and particularly preferably is (C2H4).
In the case that at least two different types of [(CnH2n)0] groups, for example [(C2H4)0], [(C3H6)0] and [(C4He)0] groups, exist in a structural unit of the formula (IV-a), they may be arranged blockwise, alternating, periodically and/or statistically, preferably blockwise and/or statistically. This means that in a structural unit of the formula (IV-a), the [(CnH2n)0] groups, and e.g. the groups [(C2H4)0], [(C3H6)0] and [(C4He)0], may be arranged, for example, in a purely statistically or blockwise form but may also be arranged in a form which could be considered as both statistical and blockwise, e.g. small blocks of [(C2H4)0] and [(C3H6)0] arranged in a statistical manner, or in a form wherein adjacent instances of statistical and blockwise arrangements of the groups [(C2H4)0], [(C3H6)0] and [(C4He)0] exist.
Within the structure element -[R3-0]f- in a structural unit of the formula (IV-a) any of the groups [(CnH2n)0], e.g. any of the groups [(C2H4)0], [(C3H6)0] and [(C4He)0], can form an end group of the structure element -[R3-0]f- This means, for example, that the two end groups of the structure element -[R3-0]f- in a structural unit of the formula (IV-a) may be formed by [(C2H4)0] groups, may be formed by [(C3H6)0] groups, may be formed by [(C4He)0] groups or may be formed by different groups selected from [(C2H4)0], [(C3H6)0] and [(C4He)0].
In the case that one molecule of the polyesters of the invention comprises two or more structural units of the formula (IV-a) the definition of R3 and “f” may vary between those structural units.
In the polyesters of the invention, the amount of the one or more terminal groups of the formula (lll-a) or mixtures thereof preferably is at least 40 wt.-%, more preferably is from 40 to 90 wt.-% and even more preferably is from 50 to 90 wt.-%, in each case based on the total weight of the polyester.
In the polyesters of the invention, the combined amount of the one or more structural units of the formula (I), and the one or more structural units of the formula (II), and the one or more terminal groups of the formula (lll-a) or mixtures thereof, and, if present, the one or more polyalkyleneglycol-derived structural units of the formula (IV-a) or mixtures thereof, preferably is at least 50 wt.-%, more preferably is at least 60 wt.-% and even more preferably is at least 70 wt.-%, in each case based on the total weight of the polyester.
Preferably, the weight average molecular weight (Mw) of the inventive polyesters is from 5000 to 20000 g/mol.
The weight average molecular weight (Mw) of the inventive polyesters may be determined by GPC analysis, preferably as detailed in the following: 10 m I of sample is injected onto a PSS Suprema column of dimensions 300 x 8 mm with porosity 30 A and particle size 10 pm. The detection is monitored at 235 nm on a multiple wavelength detector. The employed eluent is 1.25 g/l of disodium hydrogen phosphate in a 45 / 55 % (v/v) water / acetonitrile mixture. Separations are conducted at a flow rate of 0.8 ml/minute. Quantification is performed by externally calibrating standard samples of different molecular weight polyethylene glycols.
Preferably, the number of structural units of the formula (I) in the polyesters of the invention is, based on a molar average, from 2 to 60, more preferably from 2 to 40, even more preferably from 2 to 30, particularly preferably from 2 to 20 and especially preferably from 5 to 20.
The polyesters of the invention comprise one or more terminal groups of the formula (lll-a) or mixtures thereof. In addition to these one or more terminal groups or mixtures thereof, the inventive polyesters may comprise further terminal groups, preferably selected from the group consisting of -OH, -OCH2CH(CH3)OH, -0CH(CH3)CH20H and mixtures thereof. In case the polyesters of the invention comprise one or more polyalkyleneglycol-derived structural units of the formula (IV-a) or mixtures thereof, the polyesters may also comprise terminal
groups of the formula -0-[R3-0]f-H wherein R3 and “f” have the meaning given above.
Preferably, the polyester molecules of the invention comprise two or more terminal groups of the formula (lll-a) or mixtures thereof. Even more preferably, all terminal groups of the polyester molecules of the invention are terminal groups of the formula (lll-a) or mixtures thereof.
In a preferred embodiment of the invention, the inventive polyesters consist of a1 ) one or more structural units of the formula (I) and a2) one or more structural units of the formula (II) and a3) one or more terminal groups of the formula (lll-a) or mixtures thereof.
In a further preferred embodiment of the invention, the inventive polyesters consist of b1 ) one or more structural units of the formula (I) and b2) one or more structural units of the formula (II) and b3) one or more terminal groups of the formula (lll-a) or mixtures thereof, and b4) one or more polyalkyleneglycol-derived structural units of the formula (IV-a) or mixtures thereof.
For the preparation of the polyesters of the invention, typically a two-stage process is used of either direct esterification of diacids and diols or transesterification of diesters and diols, followed by a polycondensation reaction under reduced pressure.
A further subject matter of the invention is a process for the preparation of the inventive polyesters, comprising the steps of: heating one or more substances of the formula Q1-OOC-C6H4-COO-Q2, wherein Q1 and Q2, independently of one another, are selected from the group consisting of H and (Ci-C4)-alkyl and preferably are CFta, and 1 ,2-propyleneglycol, and one or more substances of the formula R1-[0-R2]a-0H or mixtures thereof, wherein R1, R2 and “a” have the meaning given above, with the addition of a catalyst, to temperatures of from
160 to 220°C, preferably beginning at atmospheric pressure, and then continuing the reaction under reduced pressure at temperatures of from 160 to 240°C.
Reduced pressure preferably means a pressure of from 0.1 to 900 mbar and more preferably a pressure of from 0.5 to 500 mbar.
Typical transesterification and condensation catalysts known in the art can be used for the inventive process for the preparation of the inventive polyesters, such as antimony, germanium and titanium-based catalysts. Preferably, tetraisopropyl orthotitanate (IPT) and sodium acetate (NaOAc) are used as the catalyst system in the inventive process for the preparation of the polyesters of the invention.
In order to obtain polyesters of the invention comprising one or more polyalkyleneglycol-derived structural units of the formula -0-[R3-0]f- (IV-a) or mixtures thereof, the respective one or more polyalkyleneglycols of the formula HO-[ R3-0]f-H or mixtures thereof, may be employed in the inventive process for the preparation of the polyesters of the invention.
The inventive polyesters may advantageously be used as soil release agents.
A further subject matter of the invention therefore is the use of one or more polyesters of the invention as soil release agents. "Soil release agent" as used herein means an agent that enhances soil removal during laundering by modifying the surface of the fabric that is laundered, preferably by increasing surface polarity.
The inventive polyesters may advantageously be used in detergent compositions.
A further subject matter of the invention therefore is the use of one or more polyesters of the invention in detergent compositions.
A further subject matter of the invention is detergent compositions comprising Z1 ) one or more polyesters of the invention and
Z2) one or more surfactants.
The inventive detergent compositions are preferably laundry detergent compositions.
The detergent compositions of the invention comprise the one or more polyesters of component Z1 ) preferably in an amount of at least 0.1 wt.-%, more preferably in an amount from 0.1 to 10 wt.-%, even more preferably in amount from 0.2 to 5 wt.-% and particularly preferably in an amount from 0.2 to 3 wt.-%, in each case based on the total weight of the detergent composition.
The detergent compositions of the invention comprise one or more surfactants as component Z2).
Surfactants assist in removing soil from textile materials and also assist in main taining removed soil in solution or suspension in the wash liquor.
Preferably, the one or more surfactants of component Z2) of the detergent compositions of the invention are selected from the group consisting of anionic, nonionic, cationic and zwitterionic surfactants, and more preferably from the group consisting of anionic, nonionic and zwitterionic surfactants.
Anionic Surfactants
Suitable anionic surfactants that may be used are any of the conventional anionic surfactant types typically used in detergent products. These include alkyl sulfonates, alkyl ether sulfates, alkyl sulfates, alkyl ester sulfonates and soaps. Preferred anionic surfactants are alkylbenzene sulfonates, alkyl ether sulfates, alkyl sulfates and soaps.
Preferred alkyl sulfonates are alkylbenzene sulfonates, particularly linear alkyl benzene sulfonates (LAS) having an alkyl chain length of Cs-C-is. Possible counter ions for concentrated alkaline liquids are ammonium ions, e.g. those generated by the neutralization of alkylbenzene sulfonic acid with one or more ethanolamines,
for example monoethanolamine (MEA) and triethanolamine (TEA), or alternatively, alkali metals, e.g. those arising from the neutralization of alkylbenzene sulfonic acid with alkali hydroxides. The linear alkyl benzene sulfonate surfactants may be LAS with an alkyl chain length of preferably from 8 to 15 and more preferably from 12 to 14. The neutralization of the acid may be performed before addition to the detergent compositions of the invention or during the process of formulating the detergent compositions of the invention through excess addition of neutralizing agent.
Preferred alkyl ether sulfates (AES) are alkyl polyethoxylate sulfate anionic surfactants of the formula
R40(C2H 0)yS03 M+ wherein
R4 is a saturated or unsaturated alkyl chain having preferably from 10 to 22 carbon atoms, and more preferably from 12 to 16 carbon atoms,
M+ is a cation which makes the compound water-soluble, preferably an ammonium cation, a substituted ammonium cation, an alkali metal cation, or other material chosen from the list of buffers, and y averages preferably from 1 to 15, more preferably from 1 to 3 and even more preferably is 3.
Preferred alkyl sulfates (AS) are surfactants of the formula
R50S03 M+ wherein
R5 is a linear or branched alkyl chain having preferably from 8 to 24 carbon atoms, and more preferably from 12 to 18 carbon atoms, and M+ is a cation which makes the compound water-soluble, preferably an ammonium cation, a substituted ammonium cation, an alkali metal cation, or other material chosen from the list of buffers.
Soaps are preferably fatty acids and more preferably linear saturated or unsatured fatty acids having from 10 to 18 carbon atoms.
Nonionic Surfactants
Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamides) such as N-methyl glucamides. Mixtures of nonionic surfactant may be used.
If included therein, the detergent compositions of the invention contain preferably from 0.2 to 40 wt.-% and more preferably from 1 to 20 wt.-% of a nonionic surfactant, such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("glucamides").
Zwitterionic Surfactants
The detergent compositions of the invention may comprise up to 10 wt.-% of a zwitterionic surfactant, e.g. amine oxide or betaine.
Typical amine oxides used are of the formula
R6N(0)(CH2R7)2 wherein
R6 is a long chain moiety and each CH2R7 are short chain moieties, and
R7 is preferably selected from the group consisting of H, CH3 and -CH2OH.
In general, R6 is a primary or branched hydrocarbyl moiety with a chain length of from 8 to 18, which can be saturated or unsaturated. Preferably, R6 is a primary alkyl moiety with a chain length of 8 to 18 carbon atoms.
Preferred amine oxides have compositions wherein R6 is a Cs-C-is alkyl and R7 is H. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
A preferred amine oxide material is lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO.
Betaines may be alkyldimethyl betaines or alkylamido betaines, wherein the alkyl groups have C12-18 chains.
In a preferred embodiment of the invention, the one or more surfactants of component Z2) of the detergent compositions of the invention are selected from the group consisting of linear alkyl benzene sulfonates, alkyl ether sulfates, alkyl sulfates, soaps, nonionic surfactants, amine oxides and betaines, and preferably the one or more surfactants of component Z2) of the detergent compositions of the invention are selected from the group consisting of linear alkyl benzene sulfonates, alkyl ether sulfates, alkyl sulfates, soaps and nonionic surfactants.
Additional Surfactants
Other surfactants than the preferred LAS, AES, AS, soaps and nonionic surfactants may be added to the mixture of detersive surfactants.
The detergent compositions of the invention comprise the one or more surfactants of component Z2) preferably in an amount of at least 3 wt.-%, more preferably in an amount from 3 to 65 wt.-%, even more preferably in an amount from 4 to 60 wt.-% and particularly preferably in an amount from 5 to 55 wt.-%, in each case based on the total weight of the detergent composition.
Further Optional Ingredients
In addition to the one or more polyesters of component Z1) and the one or more surfactants of component Z2), the detergent compositions of the invention may comprise one or more optional ingredients, e.g. they may comprise conventional ingredients commonly used in detergent compositions, especially laundry detergent compositions. Examples of optional ingredients include, but are not limited to builders, bleaching agents, bleach active compounds, bleach activators, bleach catalysts, photobleaches, dye transfer inhibitors, colour protection agents, anti-redeposition agents, dispersing agents, fabric softening and antistatic agents, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, malodour reducers, preservatives, disinfecting agents, hydrotropes, fibre lubricants, anti-shrinkage agents, buffers, fragrances, processing aids, colorants, dyes, pigments, anti-corrosion agents, fillers, stabilizers and other conventional ingredients for detergent compositions such as washing or laundry detergent compositions.
Polyalkoxylated polyethyleneimine
For detergency boosting, it is advantageous to use a second polymer alongside the one or more polyesters of component Z1 ) in the detergent compositions of the present invention. This second polymer is preferably a polyalkoxylated polyethyleneimine (EPEI). Polyethylene imines are materials composed of ethylene imine units -CFI2CFI2NFI- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.
Other Polymers
In addition to the one or more polyesters of component Z1) and the optional EPEI, the detergent compositions of the invention may comprise other polymeric materials, for example: dye transfer inhibition polymers, anti-redeposition polymers and cotton soil release polymers, especially those based on modified cellulosic materials. Especially, if EPEI is not present, the detergent compositions of the
invention may further comprise a polymer of polyethylene glycol and vinyl acetate, for example the lightly grafted copolymers described in WO 2007/138054. Such amphiphilic graft polymers based on water soluble polyalkylene oxides as graft base and side chains formed by polymerisation of a vinyl ester component have the ability to enable reduction of surfactant levels whilst maintaining high levels of oily soil removal.
Hydrotropes
In the context of this invention a hydrotrope is a solvent that is neither water nor conventional surfactant that aids the solubilisation of the surfactants and other components, especially polymer and sequestrant, in the liquid to render it isotropic. Among suitable hydrotropes there may be mentioned as preferred: monopropylene glycol (MPG), glycerol, sodium cumene sulfonate, ethanol, other glycols, e.g. dipropylene glycol, diethers and urea. MPG and glycerol are preferred hydrotropes.
Enzymes
It is preferable that one or more enzymes selected from protease, mannanase, pectate lyase, cutinase, lipase, amylase, and cellulase may be present in the detergent compositions of the invention. Less preferred additional enzymes may be selected from esterase, peroxidase and oxidase. The enzymes are preferably present with corresponding enzyme stabilizers. The total enzyme content in the detergent compositions of the invention is preferably from 0 to 5 wt.-%, more preferably from 0.2 to 4 wt.-% and even more preferably from 0.4 to 2 wt.-%, in each case based on the total weight of the detergent composition.
Sequestrants
Sequestrants are preferably included. Preferred sequestrants include organic phosphonates, alkanehydroxy phosphonates and carboxylates available under the DEQUEST trademark from Thermphos. The preferred sequestrant level is less than 10 wt.-% and preferably less than 5 wt.-% of the detergent composition of the invention. A particularly preferred sequestrant is HEDP (1-Hydroxyethylidene-1 ,1 ,- diphosphonic acid). Also suitable but less preferred as it gives inferior cleaning
results is diethylenetriamine penta(methylene phosphonic acid) (DTPMP) or Heptasodium DTPMP.
Buffers
In addition to agents optionally included for the generation of anionic surfactants, e.g. from LAS or fatty acids, the presence of buffer is preferred for pH control. Possible buffers are one or more ethanolamines, e.g. monoethanolamine (MEA) or triethanolamine (TEA). They are preferably used in the detergent compositions of the invention at levels of from 1 to 15 wt.-%, based on the total weight of the detergent composition. Other suitable amino alcohol buffer materials may be selected from the group consisting of compounds having a molecular weight above 61 g/mol, which includes MEA. Suitable materials also include, in addition to the already mentioned materials: monoisopropanolamine, diisopropanolamine, triisopropanolamine, monoamino hexanol, 2-[(2-methoxyethyl) methylamino]- ethanol, propanolamine, N-methylethanolamine, diethanolamine, monobutanolamine, isobutanolamine, monopentanolamine, 1-amino-3-(2- methoxyethoxy)-2-propanol, 2-methyl-4-(methylamino)-2-butanol and mixtures thereof.
Potential alternatives to amino ethanol buffers are alkali hydroxides such as sodium hydroxide or potassium hydroxide.
Builders
Further washing and cleaning ingredients which may be present in the detergent compositions of the invention include inorganic and/or organic builders in order to reduce the degree of hardness of the water. These builders may be present in the detergent compositions of the invention in amounts of from about 5 to about 80 wt.-%, based on the total weight of the detergent compositions. Inorganic builders include, for example, alkali metal, ammonium and alkanolammonium salts of polyphosphates, silicates, carbonates, sulfates and aluminosilicates.
Suitable organic builders include polycarboxyl compounds, such as, for example, ether polycarboxylates, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 ,3,5-trihydroxybenzene-2,4,6- trisulfonic acid and carboxymethyloxysuccinic acid, the alkali metal, ammonium and substituted ammonium salts of polyacetic acids, such as, for example, ethylenediaminetetraacetic acid and nitrilotriacetic acid, and also polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1 ,3, 5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof. Builders based on citrates, for example citric acid and its soluble salts, in particular the sodium salt, are preferred polycarboxylic acid builders, which can also be used in granulated compositions, in particular together with zeolites and/or sheet silicates.
It may be advantageous to include fluorescer and/or bleach catalyst in the detergent compositions of the invention as further high efficiency performance additives. Perfume and colorants will also desirably be included. The detergent compositions of the invention may additionally contain viscosity modifiers, foam boosting agents, preservatives (e.g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids. The detergent compositions of the invention may further comprise pearlisers and/or opacifiers or other visual cues and shading dye.
Form, packaging and dosing
The detergent compositions of the invention may be in solid or in liquid form, including a gel form. The detergent compositions of the invention may be packaged as unit doses in a polymeric film soluble in the wash water. Alternatively, the detergent compositions of the invention may be supplied in multidose plastics packs with a top or bottom closure. A dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.
The polyesters of the invention may be used in substance, i.e. as granules, but may also be provided as solutions or dispersions. The latter two exhibit beneficial handling properties and are more easily dosed. Preferably, the solutions or dispersions comprise the polyesters of the invention in an amount from 25 to 70 weight-% based on the total weight of the solution or dispersion. Suitable solvents for such solutions or dispersions are for example water, ethanol, propanol, butanol, ethylene glycol, 1,2-propylene glycol, 1 ,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, butyl glycol, butyl diglycol and butyl polyglycol. These solvents are preferably used in an amount from 25 to 75 wt.-% and more preferably in an amount from 30 to 75 wt.-%, in each case based on the total weight of the solution or dispersion. Even more preferably, the inventive solutions or dispersions comprise water and a second solvent different from water and selected from the group above.
A further subject matter of the invention is solutions or dispersions comprising one or more polyesters of the invention, preferably in an amount from 25 to 70 wt.-%, based on the total weight of the solution or dispersion, and one or more solvents selected from the group consisting of water, ethanol, propanol, butanol, ethylene glycol, 1,2-propylene glycol, 1 ,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1 ,4-butylene glycol, butyl glycol, butyl diglycol and butyl polyglycol, preferably in an amount from 25 to 75 wt.-% and more preferably in an amount from 30 to 75 wt.-%, in each case based on the total weight of the solution or dispersion. Even more preferably, the inventive solutions or dispersions comprise water and a second solvent different from water and selected from the group above.
These inventive solutions or dispersions are liquid and comprise the one or more polyesters of the invention in a high concentration. They may e.g. represent high concentrated liquid handling forms of the inventive polyesters and may be used for the preparation of inventive detergent compositions to be used by end-consumers. These inventive solutions or dispersions comprising the one or more polyesters of the invention in a high concentration nevertheless possess an advantageous low viscosity in the sense that this viscosity causes, for example, no issues on
pumpability or dosage consistency during the preparation of the inventive detergent compositions to be used by end-consumers.
The groups (C2H4) in the terminal groups of the formula (lll-a) or in the structural units of the formula (IV-a) preferably are of the formula -CH2-CH2-.
The groups (C3H6) in the terminal groups of the formula (lll-a) or in the structural units of the formula (IV-a) preferably are of the formula -CH(CH3)-CH2- or -CH2- CH(CH3)-, i.e. of the formula:
The groups (C4H8) in the terminal groups of the formula (lll-a) or in the structural units of the formula (IV-a) preferably are of the formula -CH(CH3)-CH(CH3)-, i.e. of the formula:
In the polyesters of the invention, the terminal groups or structural units of the formulae (II), (lll-a) or (IV-a) may be linked directly to structural units of the formula (I) resulting in ester groups.
It is to be understood that the polyesters of the invention are typically prepared by polycondensation processes. This leads to statistically determined mixtures of polyesters in which a mixture of molecular species with a distribution around a molar average is obtained.
The following paragraphs will show illustrative, but by no means limiting, structural entities that can be found in the polyesters of the invention.
The structural units of the formula (I) and optional additional di- or polycarboxylic acid-derived structural units are linked indirectly, preferably via the structural units of the formula (II), which - in the case of structural units of the formulae (I) and (II) results in the following structural entity:
Preferably, the terminal group of the formula (lll-a) is linked to an acyl group derived from a dicarboxylic acid, preferably to the structural unit of the formula (I), which - in the case of structural unit of the formula (I) and terminal group of the formula (lll-a) - results in the following structural entity:
Further preferred embodiments of the invention may arise from the combination of above described preferred embodiments.
EXAMPLES
The examples below are intended to illustrate the invention in detail without, however, limiting it thereto. Unless explicitly stated otherwise, all percentages given are percentages by weight (% by wt. or wt.-%).
Key to reactants used in the examples:
DMT dimethyl terephthalate
EO ethylene oxide
PG 1 , 2-propylene glycol
IPT tetraisopropyl orthotitanate
NaOAc sodium acetate
Tallow-25EO Tallow alcohol (C16/18, C18 rich, saturated (hydrogenated)) ethoxylate with 25 EO (Genapol® T 250, Clariant)
Tallow-50EO Tallow alcohol (C16/18, C18 rich, saturated (hydrogenated)) ethoxylate with 50 EO (Genapol® T 500, Clariant)
Tallow-80EO Tallow alcohol (C16/18, C18 rich, saturated (hydrogenated)) ethoxylate with 80 EO (Genapol® T 800, Clariant)
Tallow-120EO Tallow alcohol (C16/18, C18 rich, saturated (hydrogenated)) ethoxylate with 120 EO
Lauryl-80EO Lauryl alcohol (C12/14, C12 rich) ethoxylate with 80 EO
IsotridecyMOOEO Isotridecyl alcohol (C11-C14 iso alcohol, C13 rich) ethoxylate with 100 EO
Example 1 : Polyester preparation
General procedure for the preparation of the polyesters of the examples.
The polyester synthesis is carried out by the reaction of dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG) and one or more poly(alkyleneglycol)monoalkylethers or one or more poly(alkyleneglycol)monoalkenylethers or mixtures thereof (collectively “Cap”), using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as the catalyst system. The synthesis is a two-step procedure. The first step is a trans esterification and the second step is a polycondensation.
Inventive polyester example 1
38.8 g (0.2 mol) of dimethyl terephthalate (DMT), 30.4 g (0.4 mol) of 1 ,2-propylene glycol (PG), 271.6 g (0.2 mol) of Tallow-25EO and 0.5 g of sodium acetate (anhydrous) (NaOAc) are weighed into a reaction vessel at room temperature. For the melting process and homogenization, the mixture is heated up to 70°C. 200 pL (0.7 mmol) of tetraisopropyl orthotitanate (IPT) is added and the mixture is further
heated up to 170°C for 1 hour and then up to 210°C for a further 1 hour sparged by a nitrogen stream. During the transesterification methanol is released from the reaction and is distilled out of the system (distillation temperature < 55°C). After 2 hours at 210°C nitrogen is switched off and the pressure is reduced to 400 mbar over 3 hours. Subsequently, the mixture is heated up to 230°C. At 230°C, the pressure is reduced to 1 mbar over 160 minutes. Once the polycondensation reaction has started, 1,2-propylene glycol is distilled out of the system. The mixture is stirred for 4 hours at 230°C and a pressure of 1 mbar. The reaction mixture is cooled down to 140 - 150°C. Vacuum is released with nitrogen and the molten polymer is transferred out of the reactor.
Inventive polyester examples 2 to 14 are synthesized according to the general procedure as described above for inventive polyester example 1 with monomer type and dosage described below (see Table 1).
Table 1 Inventive polyester examples 1 to 14
a 400 mI_ IPT and 1.0 g NaOAc were used
Example 2: Compositions containing polyesters and their viscosity
A series of exemplary liquid laundry detergent compositions containing no polyester (reference composition A), containing a comparative polyester (comparative composition B) or containing inventive polyester (inventive compositions C-M) were prepared according to Table 2.
Key to ingredients used in the compositions of Table 2
LAS is C-12-14 linear alkylbenzene sulfonate, sodium salt
SLES 2EO is sodium lauryl ether sulfate with 2 moles EO (Genapol®
LRO, Clariant).
Nl 7EO is C-12-15 alcohol ethoxylate 7EO nonionic (Genapol®
LA070, Clariant)
Fatty Acid is a C12-18 stripped palm kernel fatty acid SRP is a polyester prepared according to examples from
Table 1
Texcare® SRN 260 is a nonionic soil release polymer (Clariant)
Table 2 - Liquid laundry detergent compositions for performance testing
a.m. active matter
The viscosities of the compositions of Table 2 were determined using a Malvern Kinexus equipped with a CP 4 40 mm, at a temperature of 25 °C and at a shear rate of 200 s 1 and rounded to the nearest 5 mPas. The appearance of the compositions was determined visually. The results are summarized in Table 3.
Table 3 - Viscosity and appearance of liquid detergent compositions
Example 3: Soil Release performance of inventive polyesters
Detergent compositions of Example 2 were tested for their soil release performance according to the “Dirty-Motor ON” Test (DMO-Test) using a Lini Apparatus under the following conditions (see Table 4).
Table 4 Conditions for testing of soil release performance
As test fabric, white polyester standard swatches (WFK 30A from WFK Testgewebe GmbFI) were used. The fabrics were prewashed three times with the liquid detergent compositions. The swatches were then rinsed, dried and soiled with 25 pi of dirty motor oil. After 1 hour the soiled fabrics were washed again with the same stored laundry detergent compositions used in the pre-washing step. After rinsing and drying the washed swatches, a measurement of the remission of the stained fabric at 457 nm was made using a spectrophotometer (Datacolor 650).
The soil release performance is shown as an improvement in soil removal of the swatches washed with a composition containing an inventive polyester as additive compared with the same composition containing no additive (Composition A)
AR Rwith additive ~R without additive
The washing results obtained for the inventive laundry detergent compositions comprising the polyesters of the invention are expressed as AR along with the standard deviations (SD) (see Table 5).
Table 5 Soil release test results
The results in Table 5 suggest that the inventive polyesters show a significant soil release effect.
Similar tests with Compositions C to H suggest that the polyesters provide a significant soil release effect.
Claims
1. A polyester comprising one or more structural units of the formula (I)
and one or more structural units of the formula (II)
and one or more terminal groups of the formula (lll-a) or mixtures thereof
(lll-a)
wherein
R1 is a linear or branched, preferably a linear, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 18 carbon atoms or mixtures thereof, and more preferably a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or a linear or branched, preferably a
linear, alkenyl group comprising one or more double bonds and from 10 to 15 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, preferably from 10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150, and
R2 is a linear or branched alkylene group (Cmhtem) with m being a number from 2 to 10 or mixtures thereof, preferably with m being a number from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (C3H6), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (C3H6) and mixtures thereof, and particularly preferably is (C2H4).
2. The polyester according to claim 1 , characterized in that R1 is selected from the group consisting of linear or branched C10-C15 alkyl, cocoyl, partially or totally hydrogenated variants of cocoyl, talloyl, partially or totally hydrogenated variants of talloyl and mixtures thereof.
3. The polyester according to claim 1 or 2, characterized in that R1 is a linear or branched, preferably a linear, alkyl group comprising from 10 to 15 carbon atoms or mixtures thereof, and even more preferably is selected from the group consisting of lauryl, myristyl and mixtures thereof.
4. The polyester according to one or more of claims 1 to 3, characterized in that it comprises one or more polyalkyleneglycol-derived structural units of the formula (IV-a)
or mixtures thereof, wherein
f is, based on a molar average, a number from 2 to 200, preferably from 10 to 200, more preferably from 20 to 150 and even more preferably from 60 to 150, and
R3 is a linear or branched alkylene group (Cnhten), with n being a number from 2 to 10 or mixtures thereof, preferably with n being a number from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (C3H6), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (C3H6) and mixtures thereof, and particularly preferably is (C2H4).
5. The polyester according to one or more of claims 1 to 4, characterized in that the amount of the one or more terminal groups of the formula (lll-a) or mixtures thereof is at least 40 wt.-%, preferably is from 40 to 90 wt.-% and more preferably is from 50 to 90 wt.-%, in each case based on the total weight of the polyester.
6. The polyester according to one or more of claims 1 to 5, characterized in that the combined amount of the one or more structural units of the formula (I), and the one or more structural units of the formula (II), and the one or more terminal groups of the formula (lll-a) or mixtures thereof, and, if present, the one or more polyalkyleneglycol-derived structural units of the formula (IV-a) or mixtures thereof, is at least 50 wt.-%, preferably is at least 60 wt.-% and more preferably is at least 70 wt.-%, in each case based on the total weight of the polyester.
7. The polyester according to one or more of claims 1 to 6, characterized in that its weight average molecular weight (M ) is from 5000 to 20000 g/mol.
8. The polyester according to one or more of claims 1 to 7, characterized in that the number of structural units of the formula (I) is, based on a molar average, from 2 to 60, preferably from 2 to 40, more preferably from 2 to 30, even more preferably from 2 to 20 and particularly preferably from 5 to 20.
9. The polyester according to one or more of claims 1 to 8, characterized in that it either a) consists of a1 ) one or more structural units of the formula (I) and a2) one or more structural units of the formula (II) and a3) one or more terminal groups of the formula (lll-a) or mixtures thereof, or b) consists of b1 ) one or more structural units of the formula (I) and b2) one or more structural units of the formula (II) and b3) one or more terminal groups of the formula (lll-a) or mixtures thereof, and b4) one or more polyalkyleneglycol-derived structural units of the formula (IV-a) or mixtures thereof.
10. A process for the preparation of a polyester according to one or more of claims 1 to 9, characterized in that it comprises the steps of: heating one or more substances of the formula Q1-OOC-C6H4-COO-Q2, wherein Q1 and Q2, independently of one another, are selected from the group consisting of H and (Ci-C4)-alkyl and preferably are Chta, and 1 ,2-propyleneglycol, and one or more substances of the formula R1-[0-R2]a-OH or mixtures thereof, wherein R1 has the meaning given in one or more of claims 1 to 3 and R2 and “a” have the meaning given in claim 1, with the addition of a catalyst, to temperatures of from 160 to 220°C, preferably beginning at atmospheric pressure, and then continuing the reaction under reduced pressure at temperatures of from 160 to 240°C.
11. The use of one or more polyesters according to one or more of claims 1 to 9 as a soil release agent.
12. A detergent composition, preferably a laundry detergent composition, comprising
Z1 ) one or more polyesters according to one or more of claims 1 to 9 and Z2) one or more surfactants.
13. The detergent composition according to claim 12, characterized in that it comprises the one or more polyesters of component Z1 ) in an amount of at least 0.1 wt.-%, preferably in an amount from 0.1 to 10 wt.-%, more preferably in an amount from 0.2 to 5 wt.-% and even more preferably in an amount from 0.2 to 3 wt.-%, in each case based on the total weight of the detergent composition.
14. The detergent composition according to claim 12 or 13, characterized in that it comprises the one or more surfactants of component Z2) in an amount of at least 3 wt.-%, preferably in an amount from 3 to 65 wt.-%, more preferably in an amount from 4 to 60 wt.-% and even more preferably in an amount from 5 to 55 wt.-%, in each case based on the total weight of the detergent composition.
15. A solution or dispersion comprising one or more polyesters according to one or more of claims 1 to 9, preferably in an amount from 25 to 70 wt.-%, based on the total weight of the solution or dispersion, and one or more solvents selected from the group consisting of water, ethanol, propanol, butanol, ethylene glycol, 1,2-propylene glycol, 1 ,3-propylene glycol, 1,2-butylene glycol, 1 ,3-butylene glycol, 1,4-butylene glycol, butyl glycol, butyl diglycol and butyl polyglycol, preferably in an amount from 25 to 75 wt.-% and more preferably in an amount from 30 to 75 wt.-%, in each case based on the total weight of the solution or dispersion and even more preferably, the solution or dispersion comprises water and a second solvent different from water and selected from the group above.
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GB1088984A (en) | 1963-06-05 | 1967-10-25 | Ici Ltd | Modifying treatment of shaped articles derived from polyesters |
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-
2021
- 2021-05-19 EP EP21726646.9A patent/EP4153710A1/en active Pending
- 2021-05-19 CN CN202180034303.3A patent/CN115551984A/en active Pending
- 2021-05-19 WO PCT/EP2021/063267 patent/WO2021233987A1/en unknown
- 2021-05-19 BR BR112022020079A patent/BR112022020079A2/en unknown
- 2021-05-19 US US17/926,058 patent/US20230183612A1/en active Pending
Also Published As
Publication number | Publication date |
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WO2021233987A1 (en) | 2021-11-25 |
CN115551984A (en) | 2022-12-30 |
BR112022020079A2 (en) | 2022-11-29 |
US20230183612A1 (en) | 2023-06-15 |
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